1. Field of the Invention
This invention relates to polyurethane compositions suited for use as coating compositions. More particularly, the invention relates to polyurethane compositions comprising a polyurethane synthesized by the reaction of a polymeric diol, a specific alicyclic organic diisocyanate, a specific alicyclic diamine and hydrazine or isophthalic acid dihydrazide in specific proportions and a solvent for said polyurethanes. These polyurethane compositions have good solution stability and, when applied as coating compositions, give coats with good light stability, good surface properties, high softening points and sufficient flexibility at low temperatures.
2. Description of the Prior Art
Because of their excellent properties with respect to resistance to damage by chemicals, abrasion resistance, toughness, cold resistance and durability, and also as a result of developments and advances of various processing techniques for them and furthermore because of their unique elasticity nature, which covers a middle region between rubbers and plastics, polyurethanes are suitable for a wide variety of uses, for example, in the production of various shaped articles, especially foamed articles such as cushion material and construction materials, elastic fibers, paints, adhesives and furthermore synthetic leather-like materials. While they have many advantages such as mentioned above, polyurethanes are poor in light stability. Specifically, they are liable to decomposition upon exposure to light, which decomposition leads to decrease in strength and elongation characteristics. Especially when polyurethanes are used in coating compositions, it is very important that they have good light resistance.
So far various methods have been proposed for the improvement of light stability, which is the most important problem to be solved for wider use of polyurethanes. Polyurethanes are generally produced by reacting a high molecular diol of the polyester or polyether or polycarbonate type, for instance, with an organic diisocyanate and an active hydrogen-containing compound, which is a chain extender. It is known that, when an aromatic organic diisocyanate is used as the organic diisocyanate or when an aromatic organic diamine is used as the active hydrogen-containing compound, the resulting polyurethanes are susceptible to degradation under the action of light. The light resistance can be improved by the use of an aliphatic or alicyclic organic diisocyanate and/or diamine in place of the aromatic organic diisocyanate and/or diamine. It is also known that polyurethanes produced with the use of hydrazine as the chain extender generally have improved light resistance.
Based on these findings, German Patent No. 2,252,280 (which corresponds to U.S. Pat. No. 3,900,688 and British Pat. No. 1,418,550) discloses that polyurethanes synthesized by using a polycarbonate glycol as the polymeric diol, a combination of an aliphatic organic diisocyanate and an alicyclic organic diisocyanate, specifically a combination of hexamethylene diisocyanate and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, as the organic diisocyanate and a combination of an alicyclic organic diamine, specifically 4,4'-diamino-dicyclohexylmethane, and hydrazine as the chain extender have excellent light resistance. The polyurethanes disclosed in the patent specification cited above, though considerably improved in light resistance, have low softening points and poor abrasion resistance and consequently are not suited for use in coating compositions.
On the other hand, U.S. Pat. No. 4,212,916 (which corresponds to British Pat. No. 2,014,593 and German Patent No. 2,905,185) discloses that polyurethanes produced by using dicyclohexylmethane-4,4'-diisocyanate, which is an alicyclic organic diisocyanate, as the organic diisocyanate and a combination of 4,4'-diaminodicyclohexylmethane, which is an alicycic organic diamine, and phthalic acid dihydrazide as the chain extender, when dissolved in an aprotic organic solvent such as dimethylformamide, give compositions having good light resistance. However, the polyurethanes described in the above-cited patent are very poor in solution stability. Specifically, the polymer solutions unfavorably increase in viscosity during polymerization or storage after polymerization and sometimes gelation takes place. Thus, the known polyurethanes are poor in solution stability, softening point, abrasion resistance and other respects and cannot give satisfactory coating compositions although they are satisfactory with respect to light resistance or light stability.